Brief introduction of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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Diversity-Oriented Synthesis of Diol-Based Peptidomimetics as Potential HIV Protease Inhibitors and Antitumor Agents

Peptidomimetic HIV protease inhibitors are an important class of drugs used in the treatment of AIDS. The synthesis of a new type of diol-based peptidomimetics is described. Our route is flexible, uses d-glucal as an inexpensive starting material, and makes minimal use of protection/deprotection cycles. Binding affinities from molecular docking simulations suggest that these compounds are potential inhibitors of HIV protease. Moreover, the antiproliferative activities of compounds 33 a, 35 a, and 35 b on HT-29, M21, and MCF7 cancer cell lines are in the low micromolar range. The results provide a platform that could facilitate the development of medically relevant asymmetrical diol-based peptidomimetics.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Direct one-pot introduction of 2-methylpyridines to Baylis-Hillman adducts via base-mediated 3-aza-Cope rearrangement

An efficient and regioselective introduction method of 2-methylpyridines to the secondary position of Baylis-Hillman adducts has been developed. A base treatment of 2-methylpyridinium salt of Baylis-Hillman bromide generated N-allylenamine intermediate which underwent a facile 3-aza-Cope rearrangement under mild conditions to produce the product.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Final Thoughts on Chemistry for (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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An efficient approach to homochiral indane nucleosides

A series of new chiral 6-substituted purinyl and 8-aza-purinyl carbonucleosides based on indanol were synthesized from the commercially available (1R,2S)-1-amino-2-indanol and (1S,2R)-1-amino-2-indanol based on a well-known methodology.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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The detection of chemically induced chromosomal malsegregation in Saccharomyces cerevisiae D61.M: A literature survey (1984-1990)

Our objective is to summarize the published data obtained with a recently developed tester strain suitable for the detection of chromosomal malsegregation in yeast. Results from 25 papers were reviewed in which numerical data for 111 chemicals tested in Saccharomyces cerevisiae D61.M are reported (a total of 316 independent tests; 279 acceptable, 37 not meeting our criteria). Of the 111 compounds analyzed 43 compounds are positive for chromosomal malsegregation, 56 compounds are negative and 12 compounds do not meet our criteria for acceptance (inconclusive). Of the 43 compounds judged positive 5 (acetone, acetonitrile, benzonitrile, ethylacetate and propionitrile) were only positive using a cold interruption protocol. Recommendations are made for standardization of methods and protocols for screening purposes. Finally, a comparison with in vitro tubulin assembly data using mammalian tubulin is presented.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Carbocationic polymerization: Mechanisms and kinetics of propagation reactions

Propagation rate constants kp in carbocationic polymerizations can be obtained through two general methods. The first one, used for decades, calculated kp from the polymerization rates and from the ionic species concentrations (ISC) measured or estimated in various ways. The second one, used during the last 10 years, is based on the diffusion-clock (DC) assumption, in which competitive reactions between propagation with the monomer and termination with another nucleophile N permit to calculate kp if termination is a diffusion-controlled reaction (with e.g. kN=k diff=3×109 L mol-1 s-1 in CH2Cl2 solution). A problem arises since the k p obtained by this last method with, e.g. styrene and isobutylene are 104 to 105 times larger than those obtained earlier in solution by the ISC method, and the aim of this article is to try to explain this discrepancy. The different methods of measurement of the second-order rate constants of propagation kp+ or kp±, respectively, on unpaired ions and ion-pairs are examined in Sections 2 and 4 and compared in Section 3 with the rate constants of model reactions. The validity of the kp+ and kp± determinations by the two methods are compared (Section 6), but results are unfortunately obtained only by the DC method for styrene, p-chlorostyrene and p-methylstyrene with kp±?109Lmol-1s-1, and by the ISC method for most other monomers with kp± between 104 and 105 L mol-1 s-1. It is shown that the large difference between these two sets of values as well as that between the parameters of ionization Ki, ki and k-i of the terminal halides in living polymerizations (Section 5) cannot be explained quantitatively by the large electrophilicity of the carbocation of these poly(styrene)s. Diffusion-controlled propagation for styrene is also in contradiction with reactivity ratios and rates of copolymerization with various monomers. The recent measurements of kp± in living polymerizations of several monomers have confirmed the validity of the kp± obtained earlier from non-living systems and based on the ionic species concentration. It is concluded that kp± for styrene should be of a similar order of magnitude. In order to have a comprehensive view interpreting all experimental results, the hypothesis has been made of competitive termination (and possibly propagation) occurring as two-steps reactions, the first step being a complexation of the growing carbocation with the nucleophile, giving a resonance stabilized complex, and the second step a unimolecular rearrangement of the complex.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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A straightforward microwave method for rapid synthesis of N-1, C-6 functionalized 3,5-dichloro-2(1H)-pyrazinones

A rapid and versatile one-pot, 2 × 10 min microwave protocol for the preparation of N-1 and C-6 decorated 3,5-dichloro-2(1H)-pyrazinones was developed. Comparable reaction sequences using classical conditions require about 1-2 days of heating. The alpha-aminonitrile was first generated in a Strecker reaction and thereafter cyclized under microwave heating. The microwave approach developed offers the possibility of efficiently generating and utilizing functionalized 3-amino-5-chloro-2(1H)-pyrazinone-N-1-carboxylic acids as beta-strand inducing core structures in a medicinal chemistry context. To illustrate the usefulness of the method, the synthesis of two novel 2(1H)-pyrazinone-containing Hepatitis C virus NS3 protease inhibitors is reported. The Royal Society of Chemistry 2009.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Brief introduction of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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Processes and intermediates for the preparation of optically active 3-amino-1-(2-thienyl)-1-propanol derivatives

Enantiomerically enriched 3-amino-1-(2-thienyl)-1-propanols of the fomulae (S)-I or (R)-I wherein R1 and R2 independently denote H, C1-6-alkyl, C5-7-cycloalkyl, aralkyl or aryl, were prepared by reducing a 3-amino-1-(2-thienyl)-1-propanone of the formula (II) wherein R1 and R2 are defined as above, using a hydrogen donor in the presence of a metal catalyst, an optically active nitrogen-containing ligand and optionally a base.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Extracurricular laboratory:new discovery of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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CONDENSATION REACTION BY METAL CATALYST

The invention relates to a method for producing an azoline compound represented by the general formula (3): wherein R1 represents an optionally substituted hydrocarbon group, an optionally substituted alkoxy group, an optionally substituted alkoxycarbonyl group, a halogen atom, a substituted amino group, a substituted carbamoyl group or an optionally substituted heterocyclic group; R3, R4, R5 and R6 may be the same or different and each represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted alkoxy group, an optionally substituted alkoxycarbonyl group, a halogen atom, a substituted amino group, a substituted carbamoyl group or an optionally substituted heterocyclic group; two arbitrary groups selected from R3, R4, R5 and R6 may bond to each other to form a ring; and Z1 represents an oxygen atom, a sulfur atom or a selenium atom; comprising reacting a carboxylic acid or a carboxylic acid derivative represented by the general formula (1): ????????R1CO2R2?????(1) wherein R1 is as defined above; R2 represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group; and R1 and R2 may bond to each other to form a ring; with an aminochalcogenide represented by the general formula (2): wherein R3, R4, R5, R6 and Z1 are as defined above; in the presence of a compound containing a group 12 metal element in the periodic table.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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The cis- and trans-Effects of Cyanide in Substitution at Platinum(II)

The cis- and trans- isomers (am = dimethylamine, pyridine, 4-cyanopyridine, 4-chloropyridine, 2-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 4-ethylpyridine, morpholine or piperidine), react rapidly with excess CN(1-) in methanol to form the corresponding cis- and trans- species which then react further to give (2-).The kinetics of the slow step, + CN(1-) -> (1-) + am, has been studied.In spite of the strong trans effect of CN(1-) the trans species are all more reactive than the corresponding cis isomers.The second-order rate constants are sensitive to the nature of am; plots of log k2 against the pKa of Ham(1+) are linear but the slope for the trans isomers (-0.27) is much greater than that for the cis isomers (-0.07).The rate constants for the displacement of o-methyl substituted pyridines are smaller than predicted from their basicity.This steric hindrance effect is much more marked in the trans isomers.The complexes with am = NH3 and NH2Me are similarly less reactive than might be predicted but the effect is the same in both isomers.The results are explained in terms of the trans effect of cyanide and its effect upon the intrinsic reactivities and nucleophilic discriminations of the substrates.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Amine degradation in CO2 capture. I. A review

Post-combustion CO2 capture based on CO2 absorption by aqueous amine solutions is the most mature gas separation technology. A main problem is amine degradation due to heat, CO2, O2, NOx and SOx. This review proposes to make a critical survey of literature concerning degradation, to list degradation products and to discuss mechanisms proposed by authors. Benchmark molecule is monoethanolamine (MEA) but diethanolamine (DEA), N-methyldiethanolamine (MDEA), piperazine (PZ) and 2-amino-2-methylpropan-1-ol (AMP) are also studied. Uses of other amines and amine blends are also considered. In the case of MEA, ammonia, N-(2-hydroxyethyl)-piperazin-3-one (HEPO) and N-(2-hydroxyethyl)-2-(2-hydroxyethylamino) acetamide (HEHEAA) are the main identified degradation products in pilot plants. Among lab studies, the most cited degradation products are ammonia, carboxylic acids, N-(2-hydroxyethyl)-formamide (HEF), N-(2-hydroxyethyl)-acetamide (HEA) and N-(2-hydroxyethyl)-imidazole (HEI) for oxidative degradation, and oxazolidin-2-one (OZD), N-(2-hydroxyethyl)-ethylenediamine (HEEDA) and N-(2-hydroxyethyl)-imidazolidin-2-one (HEIA) for thermal degradation. Numerous degradation products have been identified but some are still unknown. A lot of degradation mechanisms have been proposed but some are missing or need proofs. SOx and NOx effects are still few examined and much work remains to be done concerning volatile degradation products potentially emitted to atmosphere: their identification and their formation mechanisms need further investigations.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis